CN115491008A - Method for increasing strength of degradable plastic melt - Google Patents
Method for increasing strength of degradable plastic melt Download PDFInfo
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- CN115491008A CN115491008A CN202211301304.2A CN202211301304A CN115491008A CN 115491008 A CN115491008 A CN 115491008A CN 202211301304 A CN202211301304 A CN 202211301304A CN 115491008 A CN115491008 A CN 115491008A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/06—Biodegradable
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Abstract
The invention provides a method for enhancing the melt strength of degradable plastics, and relates to a method for modifying the degradable plastics. Which comprises the following steps: mixing the matrix, the melt reinforcing agent with the active functional group and the catalyst, adding the mixture into a double-screw extruder, and performing reactive extrusion to obtain the degradable plastic. It is applied to polylactic acid and other biodegradable plastics to greatly improve the melt strength and the thermal formability.
Description
Technical Field
The invention relates to the technical field of degradable plastic modification, in particular to a method for increasing the strength of a degradable plastic melt.
Background
The degradable plastic is a plastic which has various properties meeting the use requirements, has unchanged performance in the preservation period and can be degraded into substances harmless to the environment under the natural environment condition after use. Various degradable plastics exist, including photodegradable plastics, biodegradable plastics, photo/oxidation/full-biodegradation plastics, carbon dioxide-based biodegradable plastics, thermoplastic starch resin degradable plastics and the like.
The bio-based degradable material is one of the most effective ways to solve the white pollution at present. However, most of the bio-based degradable plastics have low melt strength due to few long-chain branches in molecular chains, insufficient strain hardening, hardness and brittleness in thermoforming, narrow processing temperature range and poor thermoformability. For example, a biodegradable plastic such as polylactic acid has low melt strength and is very difficult to foam-mold, and it is difficult to obtain a foamed molded article having a high expansion ratio. Therefore, how to improve the melt strength is one of the research hotspots in the industry.
Disclosure of Invention
In order to solve the problem of low melt strength of the bio-based degradable plastics in the background art, the method for enhancing the melt strength of the degradable plastics is applied to the bio-based degradable plastics such as polylactic acid and the like, and the melt strength and the thermoformability are greatly improved.
The specific scheme is as follows:
a method of enhancing the melt strength of a degradable plastic comprising the steps of: mixing the matrix, the melt reinforcing agent with the active functional group and the catalyst, adding the mixture into a double-screw extruder, and performing reactive extrusion to obtain the degradable plastic.
In the practice of the above embodiment, preferably, the melt enhancer with reactive functional groups is obtained by grafting monomers with reactive functional groups onto graphdine and copolymerizing the monomers with comonomers.
In the implementation of the above embodiment, preferably, the monomer with active functional group is one or more of acrylic acid, maleic anhydride, methacrylic acid or glycidyl methacrylate.
In practicing the above embodiments, preferably, the comonomer is one or more of methyl methacrylate, butyl methacrylate, or butyl acrylate.
In carrying out the above embodiment, preferably, the melt reinforcing agent with a reactive functional group is prepared by the steps of:
step one, preparing a monomer solution with an active functional group, wherein the concentration of the monomer solution is 1-5 mol/L, adding graphdiyne into the monomer solution with the active functional group according to the proportion of 1-3 g/L, and stirring to obtain a mixed liquid;
step two, performing irradiation treatment on the mixed liquid obtained in the step one by using gamma-rays, and drying to obtain monomer grafted graphite alkyne with active functional groups;
step three, adding the monomer grafted graphathiane with the active functional group obtained in the step two and a comonomer into a sodium dodecyl sulfate aqueous solution, mixing and stirring, and pre-emulsifying to obtain a pre-emulsified monomer;
step four, heating the lauryl sodium sulfate aqueous solution to 40-80 ℃ at a stirring speed of 100-300r/min, dropwise adding the pre-emulsified monomer obtained in the step three to the lauryl sodium sulfate aqueous solution for 2-6h, after dropwise adding, adding ammonium persulfate and sodium bisulfite in 3 batches, controlling the reaction temperature to 40-80 ℃, and reacting for 10-20 h to obtain a polymer emulsion;
and step five, drying the polymer emulsion to obtain the melt reinforcing agent with the active functional group.
When the above embodiment is implemented, preferably, the irradiation dose in the second step is 50 to 500kGy, and the irradiation dose rate is 10 to 200kGy/h.
When the above embodiment is implemented, preferably, the control parameters of the extruder are that the temperatures of the feeding zone, the reaction zone and the extrusion zone are 170-200 ℃, 190-240 ℃ and 200-230 ℃ respectively, and the reaction time is 1-5min.
In the implementation of the above embodiment, the weight ratio of the matrix, the melt enhancer with active functional group and the catalyst is preferably (80-100): (5-15): (2-5).
In the above embodiment, the matrix is preferably polylactic acid, polyhydroxyalkanoate, or polybutylene succinate.
In the above embodiment, preferably, the catalyst is one or more of a chromium-based catalyst, a metal carboxylate-based catalyst, a tin-based catalyst, hexamethylenetetramine or a quaternary ammonium salt-based catalyst.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for enhancing the melt strength of the degradable plastic adopts the blending extrusion process of the matrix material and the melt reinforcing agent with the active functional group by adding the melt reinforcing agent with the active functional group, controls the process conditions, and utilizes the melt reinforcing agent with the active functional group to carry out branching reaction on the molecules of the matrix material in the reactive screw, thereby increasing the number of long-chain branches of the matrix material and greatly improving the melt strength and the hot formability.
2. The melt reinforcing agent with the active functional group is applied to the bio-based degradable plastic, can be well dispersed in the matrix material and intertwined with molecules of the matrix material, greatly improves the melt strength of the bio-based degradable plastic, better improves the processing performance of the bio-based degradable plastic and improves the thermal formability of the bio-based plastic.
3. The melt reinforcing agent with the active functional group, which is added in the method for reinforcing the melt strength of the degradable plastic, takes the graphite alkyne as a carrier, so that on one hand, the dispersibility of the melt reinforcing agent with the active functional group in a matrix material can be improved, and the melt reinforcing agent with the active functional group can fully react with the matrix material under a catalytic system, and on the other hand, the graphite alkyne has a conjugated large pi-bond structure, so that the capturing capability on free radicals is strong, and the thermal stability of the degradable plastic can be improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents of the examples and comparative examples are illustrated below:
matrix: polylactic acid, zhejiang sea Zhengsheng;
catalyst: tetra-n-butylammonium chloride, anhui Si and Purpurian chemical industry;
monomer with active functional group: maleic anhydride, and colorful chemical industry of Jinan;
comonomer(s): methyl methacrylate, shandong brocade chemical industry;
graphite alkyne: krama er.
It should be noted that the reagents or apparatuses used in the examples are not indicated by the specific techniques or conditions described in the literature in the field or by the product specifications, and are all conventional products commercially available.
Example 1
A method for enhancing the melt strength of degradable plastics, comprising the steps of:
adding a monomer with an active functional group into acetone to prepare a solution with the concentration of 1mol/L, adding graphdiyne according to the proportion of 1g/L, stirring for 15min, and dispersing in an ultrasonic disperser for 30min to obtain a mixed liquid;
step two, performing irradiation treatment on the mixed solution obtained in the step one by using gamma-rays, wherein the irradiation dose is 50kGy, the irradiation dose rate is 10kGy/h, performing suction filtration and irradiation to obtain a sample, repeatedly cleaning a filtered substance, drying the filtered substance in a vacuum oven at 60 ℃, and drying to obtain the monomer grafted graphite alkyne with the active functional group;
step three, adding 1 part of monomer grafted graphite alkyne with active functional groups obtained in the step two and 15 parts of comonomer into 100 parts of lauryl sodium sulfate aqueous solution with volume fraction of 1 percent in terms of weight fraction, mixing and stirring for 20min, and pre-emulsifying to obtain pre-emulsified monomer;
step four, heating 100 parts of lauryl sodium sulfate aqueous solution with volume fraction of 1% to 40 ℃ at a stirring speed of 100r/min in a nitrogen atmosphere, dropwise adding 100 parts of the pre-emulsified monomer obtained in the step three to the lauryl sodium sulfate aqueous solution, dropwise adding for 2 hours, after dropwise adding, adding 0.01 part of ammonium sulfate and 0.005 part of sodium bisulfite in 3 batches, controlling the reaction temperature at 40 ℃, and reacting for 10 hours to obtain polymer emulsion;
step five, drying the polymer emulsion to obtain a melt reinforcing agent with an active functional group;
and step six, mixing 80 parts of matrix, 5 parts of melt reinforcing agent with active functional groups obtained in the step five and 2 parts of catalyst, adding the mixture into a double-screw extruder, controlling the temperature of a feeding zone, a reaction zone and an extrusion zone of the double-screw extruder to be 170-200 ℃, 190-240 ℃ and 200-230 ℃ respectively, and reacting for 1min, and extruding to obtain the polylactic acid material.
Example 2
A method for enhancing the melt strength of degradable plastics, comprising the steps of:
adding a monomer with an active functional group into acetone to prepare a solution with the concentration of 2mol/L, adding graphdiyne according to the proportion of 1.5g/L, stirring for 15min, and dispersing in an ultrasonic disperser for 30min to obtain a mixed liquid;
step two, performing irradiation treatment on the mixed solution obtained in the step one by using gamma-rays, wherein the irradiation dose is 200kGy, and the irradiation dose rate is 100kGy/h, performing suction filtration and irradiation to obtain a sample, repeatedly cleaning a filtered substance, drying the filtered substance in a vacuum oven at 60 ℃, and drying to obtain the monomer grafted graphite alkyne with the active functional group;
step three, adding 4 parts of monomer grafted graphite alkyne with active functional groups obtained in the step two and 20 parts of comonomer into 100 parts of lauryl sodium sulfate aqueous solution with volume fraction of 1% in parts by weight, mixing and stirring for 20min, and pre-emulsifying to obtain a pre-emulsified monomer;
step four, heating 100 parts of lauryl sodium sulfate aqueous solution with volume fraction of 1% to 50 ℃ at a stirring speed of 180r/min in a nitrogen atmosphere, dropwise adding 100 parts of the pre-emulsified monomer obtained in the step three to the lauryl sodium sulfate aqueous solution, dropwise adding for 3 hours, after dropwise adding, adding 0.01 part of ammonium sulfate and 0.005 part of sodium bisulfite in 3 batches, controlling the reaction temperature at 50 ℃, and reacting for 14 hours to obtain polymer emulsion;
step five, drying the polymer emulsion to obtain a melt reinforcing agent with active functional groups;
and step six, mixing 88 parts of matrix, 8 parts of melt reinforcing agent with active functional groups obtained in the step five and 3 parts of catalyst, adding the mixture into a double-screw extruder, controlling the temperature of a feeding zone, a reaction zone and an extrusion zone of the double-screw extruder to be 170-200 ℃, 190-240 ℃ and 200-230 ℃ respectively, and reacting for 3min, and extruding to obtain the polylactic acid material.
Example 3
A method for enhancing the melt strength of degradable plastics, comprising the steps of:
adding a monomer with an active functional group into acetone to prepare a solution with the concentration of 4mol/L, adding graphite alkyne according to the proportion of 2.5g/L, stirring for 15min, and dispersing in an ultrasonic disperser for 30min to obtain a mixed liquid;
step two, performing irradiation treatment on the mixed liquid obtained in the step one by using gamma-rays, wherein the irradiation dose is 400kGy, and the irradiation dose rate is 150kGy/h, performing suction filtration and irradiation to obtain a sample, repeatedly cleaning the filtered substance, drying the filtered substance in a vacuum oven at 60 ℃, and drying to obtain the monomer grafted graphdiyne with the active functional group;
adding 8 parts by weight of monomer grafted graphite alkyne with active functional groups obtained in the step two and 25 parts by weight of comonomer into 100 parts by volume of 1% sodium dodecyl sulfate aqueous solution, mixing and stirring for 20min, and pre-emulsifying to obtain a pre-emulsified monomer;
step four, heating 100 parts of lauryl sodium sulfate aqueous solution with the volume fraction of 1% to 60 ℃ at the stirring speed of 250r/min in the nitrogen atmosphere, dropwise adding 100 parts of the pre-emulsified monomer obtained in the step three to the lauryl sodium sulfate aqueous solution for 5 hours, after dropwise adding, adding 0.5 part of ammonium sulfate and 0.01 part of sodium bisulfite in 3 batches, controlling the reaction temperature at 60 ℃, and reacting for 18 hours to obtain polymer emulsion;
step five, drying the polymer emulsion to obtain a melt reinforcing agent with an active functional group;
and step six, mixing 100 parts of matrix, 12 parts of melt reinforcing agent with active functional groups obtained in the step five and 5 parts of catalyst, adding the mixture into a double-screw extruder, controlling the temperature of a feeding zone, a reaction zone and an extrusion zone of the double-screw extruder to be 170-200 ℃, 190-240 ℃ and 200-230 ℃ respectively, and reacting for 5min, and extruding to obtain the polylactic acid material.
Example 4
A method for enhancing the melt strength of degradable plastics, comprising the steps of:
adding a monomer with an active functional group into acetone to prepare a solution with the concentration of 5mol/L, adding graphite alkyne according to the proportion of 3g/L, stirring for 15min, and dispersing in an ultrasonic disperser for 30min to obtain a mixed liquid;
step two, performing irradiation treatment on the mixed solution obtained in the step one by using gamma-rays, wherein the irradiation dose is 500kGy, the irradiation dose rate is 200kGy/h, performing suction filtration and irradiation to obtain a sample, repeatedly cleaning a filtered substance, drying the filtered substance in a vacuum oven at 60 ℃, and drying to obtain the monomer grafted graphite alkyne with the active functional group;
step three, adding 10 parts of monomer grafted graphite alkyne with active functional groups obtained in the step two and 30 parts of comonomer into 100 parts of lauryl sodium sulfate aqueous solution with volume fraction of 1% in terms of weight fraction, mixing and stirring for 20min, and pre-emulsifying to obtain pre-emulsified monomer;
step four, heating 100 parts of lauryl sodium sulfate aqueous solution with the volume fraction of 1% to 80 ℃ at a stirring speed of 300r/min in a nitrogen atmosphere, dropwise adding 100 parts of the pre-emulsified monomer obtained in the step three to the lauryl sodium sulfate aqueous solution for 6 hours, after dropwise adding, adding 0.5 part of ammonium sulfate and 0.01 part of sodium bisulfite in 3 batches, controlling the reaction temperature at 80 ℃, and reacting for 20 hours to obtain polymer emulsion;
step five, drying the polymer emulsion to obtain a melt reinforcing agent with active functional groups;
and step six, mixing 100 parts of matrix, 15 parts of melt reinforcing agent with active functional groups obtained in the step five and 5 parts of catalyst, adding the mixture into a double-screw extruder, controlling the temperature of a feeding zone, a reaction zone and an extrusion zone of the double-screw extruder to be 170-200 ℃, 190-240 ℃ and 200-230 ℃ respectively, and reacting for 5min, and extruding to obtain the polylactic acid material.
The polylactic acid particles obtained in examples 1 to 4 and the blank polylactic acid were dried in a vacuum oven at 80 ℃ for 12 hours, and then the Melt Strength (MS) thereof was measured. The test results are shown in table 1 below:
TABLE 1
According to the test results in table 1, the melt strength of the polylactic acid of examples 1 to 4 is significantly improved compared to the blank polylactic acid, thereby demonstrating that the method for enhancing the melt strength of the degradable plastic of the present invention significantly improves the melt strength of the polylactic acid.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for enhancing the melt strength of degradable plastics, which is characterized by comprising the following steps: mixing the matrix, the melt reinforcing agent with the active functional group and the catalyst, adding the mixture into a double-screw extruder, and performing reactive extrusion to obtain the degradable plastic.
2. The method for enhancing the melt strength of the degradable plastic according to claim 1, wherein the melt reinforcing agent with the active functional group is obtained by grafting the monomer with the active functional group onto a graphite alkyne and copolymerizing the graphite alkyne and the comonomer.
3. The method for enhancing the melt strength of degradable plastics according to claim 2, wherein said monomer with active functional group is one or more of acrylic acid, maleic anhydride, methacrylic acid or glycidyl methacrylate.
4. The method for enhancing the melt strength of degradable plastics according to claim 2, wherein said comonomer is one or more of methyl methacrylate, butyl methacrylate or butyl acrylate.
5. The method for enhancing the melt strength of degradable plastics according to claim 2, wherein the step of preparing the melt reinforcing agent with active functional group comprises:
step one, preparing a monomer solution with active functional groups, wherein the concentration of the monomer solution is 1-5 mol/L, adding graphite alkyne into the monomer solution with active functional groups according to the proportion of 1-3 g/L, and stirring to obtain a mixed liquid;
step two, performing irradiation treatment on the mixed liquid obtained in the step one by using gamma-rays, and drying to obtain monomer grafted graphite alkyne with active functional groups;
step three, adding the monomer grafted graphite alkyne with the active functional group obtained in the step two and a comonomer into a sodium dodecyl sulfate aqueous solution, mixing and stirring, and pre-emulsifying to obtain a pre-emulsified monomer;
step four, heating the lauryl sodium sulfate aqueous solution to 40-80 ℃ at a stirring speed of 100-300r/min, dropwise adding the pre-emulsified monomer obtained in the step three to the lauryl sodium sulfate aqueous solution for 2-6h, after dropwise adding, adding ammonium persulfate and sodium bisulfite in 3 batches, controlling the reaction temperature to 40-80 ℃, and reacting for 10-20 h to obtain a polymer emulsion;
and step five, drying the polymer emulsion to obtain the melt reinforcing agent with the active functional group.
6. The method for enhancing melt strength of degradable plastics according to claim 5, wherein in step two, the irradiation dose is 50-500 kGy and the irradiation dose rate is 10-200 kGy/h.
7. The method for enhancing the melt strength of the degradable plastic according to claim 1, wherein the control parameters of the extruder are that the temperature of the feeding zone, the temperature of the reaction zone and the temperature of the extrusion zone are respectively 170-200 ℃, 190-240 ℃, 200-230 ℃ and the reaction time is 1-5min.
8. The method for enhancing the melt strength of the degradable plastic according to claim 1, wherein the weight ratio of the matrix, the melt reinforcing agent with the active functional group and the catalyst is (80-100): (5-15): (2-5).
9. The method for enhancing the melt strength of degradable plastics according to claim 1, wherein said matrix is polylactic acid, polyhydroxyalkanoate or polybutylene succinate.
10. The method for enhancing the melt strength of degradable plastics according to claim 1, wherein the catalyst is one or more of chromium-based catalyst, metal carboxylate-based catalyst, tin-based catalyst, hexamethylenetetramine or quaternary ammonium salt-based catalyst.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103626982A (en) * | 2013-11-04 | 2014-03-12 | 上海富元塑胶科技有限公司 | Method for improving melt strength of polyester resin |
| CN104193879A (en) * | 2014-08-23 | 2014-12-10 | 山西省化工研究所（有限公司） | Melt reinforcing agent with functional group as well as preparation and application of melt reinforcing agent |
| CN113402678A (en) * | 2021-06-17 | 2021-09-17 | 华南理工大学 | Method for preparing high-melt-strength polylactic resin through two-step reaction |
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- 2022-10-24 CN CN202211301304.2A patent/CN115491008A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626982A (en) * | 2013-11-04 | 2014-03-12 | 上海富元塑胶科技有限公司 | Method for improving melt strength of polyester resin |
| CN104193879A (en) * | 2014-08-23 | 2014-12-10 | 山西省化工研究所（有限公司） | Melt reinforcing agent with functional group as well as preparation and application of melt reinforcing agent |
| CN113402678A (en) * | 2021-06-17 | 2021-09-17 | 华南理工大学 | Method for preparing high-melt-strength polylactic resin through two-step reaction |
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